The Hydrols.

Abstract

Liquid water is recognized as being more or less polymerized ( 7), but very little use is made of this except to account for the temperature of maximum density of water and for its not boiling at 80-193°K. as calculated by van't Hoff, Walden, Tammann, and Sidgwick. In many thermodynamical reasonings the assumption is made tacitly that the degree of polymerization does not change. Very few people are interested in the probability of the different forms of liquid water having different properties. This is the more remarkable because we are quite used to marked changes with different metamers and polymers.We have red N02 and colorless N204; soluble and insoluble sulfur; anthracene and dianthracene; red phosphorus and white phosphorus; diamond and graphite; cyanic acid, cyanuric acid, and cyamelid; acetaldehyde and paraldehyde; oxygen and ozone; ordinary and nascent hydrogen, oxygen, and nitrogen. The enol and keto forms can be distinguished.Polymerized alcohol peptizes pyroxylin while depolymerized alcohol does not. The two forms of chromic chloride and of benzaldoxime each lower the melting point of the other. The dielectric constant of solid nitrobenzene I is nearly four times that of solid nitrobenzene II.The lyotropic or Hofmeister series of chloride, bromide, and iodide is found to hold both for true solutions and for colloidal solutions. In the case of true solutions the series holds for reaction velocity experiments (neutral salt effect), electromotive forces, boiling points, and displacements of the temperature of maximum density. Sodium chloride increases the dissociation constant ( 18) of carbonic acid one thousandfold. Sodium chloride increases the apparent strength of boric acid (16). The apparent molecular weights of sodium chloride, bromide, and iodide vary in that order. The potential difference between hydrogen and hydrochloric acid differs from that between hydrogen and hydrobromic acid (26). Richards and Rowe (19) found that the heats of neutralization of caustic soda and caustic potash decrease as the neutralizing acid changes from hydrochloric acid to hydrobromic acid and then to hydriodic acid. The solubility of gases in salt solutions, the heat capacity of water, the displacement of the temperature of maximum density of water, and the quenching of fluorescence in certain solutions by salts show the same general phenomenon.

Lyotropic Order and the Effects of Sodium Salts on the Miscibility of Cyclohexane and Methyl Alcohol.

“…The solubility of these salts in methyl alcohol, although less than in water, is still high, and again strong solvent attraction is suggested. The data (14,15) in table 3 show that the order in which the solubilities increase is the same as the lyotropic order obtained with the cyclohexane-methyl alcohol system. Bromides, iodides, and thiocyanates show remarkable solubility in many solvents of intermediate dielectric constant.…”

Studies on the Lyotropic Series. II. The Adsorption of Salts on Gelatin.

“…Corresponding values for the hydration of gelatin obtained by other methods are: (1) 55 per cent, from the amount of water that cannot be frozen in the jelly (23); (a) 44 to 51 per cent, from the amount of water that is not free to hydrate cobaltous chloride (10); (3) 50 to 55 per cent, from the minimum amount of water present in the gelatin, which causes the volume contraction on swelling in water to be reduced to zero (14). b…”

“…A Donnan correction, however, will be appreciable only if two conditions are simultaneously fulfilled: (1) Appreciable positive true adsorption. Where there is zero or negative apparent adsorption, no Donnan correction need be expected.…”

“…Another possible type of combination is that consequent upon the 1 The isotherms of the copper salts are initially much steeper than those of the other salts. hydrolysis of the salt, whereby either the acid or the base produced, or both, may be adsorbed.…”

“…Other authors prefer to call the insoluble dried gelatin "pseudocollagen." This distinction is, however, most probably immaterial, since most investigators are today agreed that collagen is not chemically different from gelatin, and that the different physical properties are due rather to a difference in micellar 1 The experiments of these authors were carried out in mixtures of water and alcohol. A comparison of the adsorption in such mixtures with phenomena in aqueous systems is open to criticism.…”